The Rate and Mechanism of the Partial Oxidation of Acetaldehyde by PPM Concentrations of Nitrogen Dioxide

Citation

Davis, Allyn Merrill (1969) The Rate and Mechanism of the Partial Oxidation of Acetaldehyde by PPM Concentrations of Nitrogen Dioxide. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/DC6G-XN83. https://resolver.caltech.edu/CaltechTHESIS:02012016-095046535

Abstract

The thermal reaction between nitrogen dioxide and acetaldehyde in the gas phase was investigated at room temperature and atmospheric pressure. The initial rate of disappearance of nitrogen dioxide was 1.00 ± 0.03 order with respect to nitrogen dioxide and 1.00 ± 0.07 order with respect to acetaldehyde. An initial second order rate constant of (8.596 ± 0.189) x 10^-3 1.mole^-1 sec^-1 was obtained at 22.0 ± 0.1 °C and a total pressure of one atmosphere. The activation energy of the reaction was 12,900 cal/mole in the temperature range between 22°C and 122°C.

The products of the reaction were nitric oxide, carbon dioxide, methyl nitrite, nitromethane and a trace amount of trans-dimeric nitrosomethane. The addition of nitric oxide increased the rate of formation of nitromethane and decreased the rate of formation of methyl nitrite. There were no measurable surface effects due to the addition of glass wool or glass beads to the reactor.

Reactants and products were analyzed by gas chromatography. A mechanism was proposed incorporating the principal features of the reaction.

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